Process for breaking petroleum emulsions



PROCESS FOR BREAKING PETROLEUM EMULSIONS 5 Sheets-Sheet 1 Filed July 11,1950 FIG. I.

6O I40 I60 200 mu ZOFQEKME mo xmoz m O 0 O 0 O O wowmrwwwwmwo987b 9 9 99 9 9 9 9 9 9 8 8 8 8 8 4 fi .fi .44. Lr lllllllll-ll l l llll i B A/ 7L 000000 0000000 wmmawwmmmm TIME IN MINUTES POLYMERIZATION OFALLYLSUCROSE AT 100C.

INVENTOR.

Nov. 13, 1951 DE GROOTE 2,574,544

PROCESS FOR BREAKING PETROLEUM EMULSIONS Filed July 11, 1950 ,3Sheets-Sheet 2 BLOWN ALLYL c H o SUCROSE Z INVENTOR Nov. 13, 1951 M DEGROOTE 2,574,544

PROCESS FOR BREAKING PETROLEUM EMULSIONS Filed July 11, 1950 5Sheets-Sheet 5 FIG.3.

100% PROPYLENE 160% ETHYLENE OXIDE IOO'ZPOLYMER OBTAINED FROMALLYLSUCROSE OR MIXTURE OF ALLYLSUCROSE AND OTHER ALLYL COMPOUNDS I NVENTOR,

Patented Nov. 13, 1951 PROCESS FOR BREAKING PETROLEIM EMULSIONS MelvinDe Groote, University City, Mo., assignor to Petrolite Corporation,Ltd., Wihnington, DeL, a corporation of Delaware ApplicationJuly 11,1950, Serial No. 173,047

15 Claims. (Cl.252--331) This invention relates. to. processes orprocedures particularly adapted for preventing,.breaking or resolvingemulsions of the water-in-oil type, and particularly petroleumemulsions.

Complementary to the above. aspect of the invention herein disclosed ismy companion invention concerned with, the new chemical products orcompounds used as thedemulsifying agents in said aforementionedprocesses or procedures, as well astheapplication of such chemicalcompounds, products, or the like, in various other arts and industries,along with the method for manufacturing .said new chemical products orcompounds which are of outstanding value in demulsification. See myco-pending application, Serial No. 173,048,, filed July 11, 1950.

My invention provides an economical and rapid process for resolvingpetroleum emulsions.

of the water-in-oil type that are commonly referred to as cut oil, roilyoil, emulsified oil,. etc., and which comprise fine droplets ofnaturally-occurring waters or brines dispersed in a more or lesspermanent state throughout the oil which constitutes the continuousphase of the emulsion.

It also provides an economical and rapid process for separatingemulsions which have been prepared under controlled conditions frommineral oil, such as crude oil and relatively soft waters or weakbrines. Controlled emulsification and subsequent demulsification underthe conditions just mentioned are of significant value in removingimpurities, particularly inorganic salts, from pipeline oil.

Demulsification as contemplated in the present application includes thepreventive step of commingling the demulsifier with the aqueouscomponent which would 'or might subsequently become either phase of theemulsion in the absence of such precautionary measure. Similarly, suchdemulsifier may be mixed with the hydrocarbon component. I

; products of (a) an alpha-beta alkylene oxide selected from the classconsisting of ethylene oxide, propylene oxide, butylene oxide, glycide,

methyl-glycide, methyl glycidyl ether, ethyl glycidyl ether and propylglycidyl ether; and (b) an organic solvent-soluble,oxyalkylationsusceptible polymerization product of a member of the classconsisting of allylsucrose, and allylsucrose in combination with otherco-polymerizable allyl compounds.

Sub-generically the present invention is concerned with breakingpetroleum emulsions of the water-in-oil type characterized by subjectingthe emulsion to the action of a demulsifier including hydrophilesynthetic products; said hydrophile synthetic products beingoxyalkylation products of (A), an alpha-beta oxide selected from theclass consisting of ethylene oxide, propylene oxide, butylene oxide,glycide and methylglycide; and (B) an organic solvent-soluble,oxalkylation-susceptible, polymerization product of allylsucrose inwhich there is present a plurality of allyl radicals; and with the finalproviso that the hydrophile properties of said oxyalkylated derivativein an equal weight of xylene are suflicient to produce an emulsion whensaid xylene solution is shaken vigorously with one to three volumes ofwater.

The preferred aspect of the invention is concerned with oxyalkylationproducts in which the weight percentage of allylsucrose is not less than10% and not over and the molecular weight of the oxyalkylation productson an average statistical basis, assuming completeness of reaction, isin excess of 10,000.

A sub-generic aspect of the present invention which represents aninvention within an invention is described in my co-pendingapplications, Serial Nos. 146,483, and 146,484, filed February 27, 1950.v

For convenience, whatis said hereinafter is divided into four parts: I

Part 1 is concerned with the preparation of allylsucrose and thedescription of other allyl compounds which are co-polymerizable withallylsucrose Part 2 is concerned with the polymerization or blowing ofallylsucrose, or co-polymerizable mixtures of allylsucrose or otherallyl derivatives;

Part 3 is concerned with the axyalkylation of the polymerized or blownallylsucrose or allylsucrose mixtures, and

Part 4 is concerned with the use of oxyalkylated polymerizedallylsucrose or allylsucrose mixtures in resolving or breaking petroleumemulsions of the water-in-oil type.

PART 1 The preparation of allylsucrose has been described in theliterature. See Industrial and Engineering Chemistry, volume 41, p.1697, August 1949, and Sugar, volume 42, No. 9, p. 28

' lowed to cool.

(1947) It has been described also in a pamphlet distributed by the SugarResearch Foundation, Inc., 52 Wall Street, New York city, N. Y.,entitled Preparation and Properties of Allyl Sucrose.

It is expected that this product will be available commercially within areasonably short period of time. At the moment, however, pilot plantquantities are available. For convenience, what is said hereinafter issubstantially a verbatim quotation from the article in Industrial andEngineering Chemistry, cited above, and in which the authors were Ziefand Yanovsky.

Allyl Chloride Method: Two autoclaves were used. One was glass-linedwith iron fittings, the

other Monel metal. The amount of allyl chloride (and equivalent amountof alkali) was varied in an attempt to find the optimum ratio of rea'gents. Table I gives the results.

Table I.Prepa1'ation of allylsucrose with allyl chloride As with allylbromide, apparently theoptimum amount or allyl chloride is lz moles permole of sucrose. Allylsucrose was prepared as Ionows:

1. Sucrose (loco grams, 2.9 moles) was added with mechanical stirring toa mixture oi 19.02 grams (30.0 moles) or sodium hYCllOXlUE and "100 ml.or water at room temperature in a z-gahon, glass-lined autoclaveequipped with a stirrer and "a acket connected to steam and cold waterinlets.

I water at room temperature in a l-gallon,

' jacketed, Monel metal autoclave.

(1340 grams, 17.5 moles) was added, and the Allyl chloride (4680grams,35.0 moles) was then added, and the autoclave was sealed andheated to 85 C. (Jacket temperature). At the beginning of the reactionand-up to about to a valve at the top of the autoclave remained openuntil the vapors of allyl chloride started to condense at the tip of thevalve. Heating duringthe initial stage of the reaction was carefullycontrolled, since the reaction is exothermic and a rise in temperatureabove 83 C. darkens the product considerably. Within 1.5 hours thethermometer well temperature was 82 0., and the internal pressureincreased rapidly to 20 per square inch. At this point cold water wascirculated through the jacket to moderate 'the reaction. After thisexothermic stage was passed, the well temperature was easily controlledat 80 to 82C., for 5.5 hours longer. At the end of 8 hours the welltemperature was 81 C., and the pressure was down to about 4. pounds.Heating was discontinued at this point, and the autoclave was al- Theautoclave was then opened and filled with Water, with stirring, todissolve the sodium chloride. The organic layer was separated,steam-distilled, washed with water and treated as described for theallyl bromide preparation. The yield of light brown oil was v140i) grams(83.5% of theoretical) with a refractive index (11. of 1.4920. Itcontained 5.8 allyl groups and 1.9 hydroxyl groups.

2. Sucrose (500 grams, 1.5 moles) 'was added -with motor stirring to amixture of 701 grams (17.5 moles) of sodium hydroxide and .350 ml. .of

alcohol and a reactive halogen. ration of diallyl .glycerol v inftheabove noted Journalof American Chemical Society reference.)

Allyl chloride autoclave was sealed and heated to 55 C. (Jacket temerature) 101 8 hours. Because of the better heat transier or thisautoclave, it was not necessary at any time to cool the Jacket "tomoderate the reaction.

the well temperature was 82 C. At the end of is hours .the pressure wasdown to about 4 pounds and the well temperature was 78 C. The autoclavewas then cooled and filled with water to -0.1SSU1VUS-16'SOQil1m-0l'l1OIiCl, and the product was I treated as described above.

The yield 01' light brown oil was "(83 grams or theoretical), The number01' allyl groups was 5. the number or hyoroxyl groups, 1.7.

The allyl content was determined as described previously the nydroxylcontent was determined by the method described by Og Porter, andwillits.

AS has been pointed out previously allylsucro'se can be polymerizedalone or in comunction with other well known polymerizable allylcompounds. Such other allyl compounds which can no employed in admixturewith allylsucrosezmay :or may not contain hydroxyl radicals, orIorzthatmatter,

some other radical .such :as a zcarboxylradicalor a radical withhydrogen bound rto mtrogen which is also susceptible to oxyalkylatio'n.Some of these compounds will be ldescri'oedssubsequently -but inthe mainthe procedure of preparing such compound is well known. .In connectionwith such allyl derivatives reference is .made .to, a

pamphlet entitled Ally'l Alcohol, .issuedby. Shell ChemicalCorporation,;500 Fifth Avenue, New York 18, N. Y., 1946. 'SeealsoJournal American See also Data Sheet DS-48:22, fAllyl Glycidyl Ether,shell Chemical Company, 500 Fifth Avenue, New York '18, NY.

Various methods employed for producing suitable allylcompouhds includethe following:

-(1) The esterifica-tion of allyl alcohol with a ,monocarboxy acid suchas 'a higher fattyacid, including oleic a'cid, ricinoleic acid, etc.

2") The esterificat-ion of allylalcohol withthe 'erol monophthalate,etc.

(3) The reaction involving 'alkoxide and allyl chloride '(seemanufacture of allylsucrose above).

(4) The reaction involving the alkoxi'de of allyl (5.) The use involvingv1-allyloxy- 3-chloro-2- propanol.

.(6). Reactions involving compounds such as 1,3-dichloropropene.

.(7) Allyl alcohol .can be treated with alkylene' .oxides, such asethylene oxide, propylene :oxide, butylene.oxide, glycide, etc. Theresidual hydroxyl group can be used as an intermediate for furtherreaction. Allyl alcoholcan be treated also with epichlorohydrin, orsimilar-chloro-epoxy compounds, so .as to give derivatives in which 1Nichols, EP.'L., Jr., and anovsky, Elias, J. chem.

Soc, :67, 4Q 1945). r I 2 gg, L. Porter W. L., and'Willits, C. 0.,Ind.Eng. -Chem., Anal. ltd, it, 394 1945 Within 1.75 hours the internalpressure reached 25 pounds per square 1110111,. and.

(See :the proper further reaction may involve not only the hydroxylradical but also the chlorine atom, or both. "(8)'Numerous otherreactions are included in the literature and particularly the patentliterature of allyl resins. In many instances the most satisfactoryprocedure is to employ allyl glycidyl ether(1allyloxy-2,3-epoxypropane).

Subsequently there is described in Part 3 procedures involvingoxyalkylation, and particularly oxyalkylation'involving the use ofglycide. The use of allyl glycidyl ether is comparable to the use ofglycide. Inother words, in the properly chosen reactions a double bondis not involved but only the high reactivity of the epoxide group. Like'glycide, or for that matter any other reactive alkylene oxide, allylglycidyl ether generally does not require the use of a catalyst,particularly an alkaline catalyst, when used in connection with basicnitrogen compounds for instance a reaction involving triethanolamine. 11 In the treatment of suitable reactants with allyl glycidyl ether thesame precaution should be taken, or even greater precaution, than in theuse of glycide. If in doubt an initial exploratory synthesis should beundertaken with due precaution and particularly with a means ofcontrolling the heat involved so the speed of reaction can becontrolled. Suitable reactants for reaction with allyl glycidyl etherare so numerous that they may be simply indicated as substantially allthose which are reactive towards glycide. Generally speaking, thisincludes almost all compounds having a reactive hydrogen (hydrogenattached to nitrogen, oxygen or sulfur) and in some instances compoundsnot apparently showing a reactive hydrogen atom.. Particularly suitableare materials such as glycerol, diglycerol, higher polyglycerols,sucrose, sorbitoljsorbitan, mannitol, mannitan, etc. Similarlyone mayemploy the same compounds which have been treated with an alkylene oxideother than allyl glycidyl ether, such as ethylene oxide, propyleneoxide, glycide, etc.

, Other compounds particularly suitable include pentaerythritols,'polypentaerythritols, glycose, sugar derivatives such as glycolglucosides of the kind described in U. S. Patents 2,407,001, 2,407,002,and 2,407,003, dated September 3, 1946, to Grifiin, tetramethylolcyclohexanol, and allyl starch.

Other materials which may be treated with alkylene oxides so as tochange their nature and particularly so as to render them morehydrophile and usually Water-soluble, are described in numerous patents,such as British Patents Nos. 341,516,- 364,323, 368,530, 380,851, and411,474. .(See also U. S. Patent No. 1,596,785, dated August 17, 1926,to Weyland.) The materials so included cover such diverse products asglue, gelatin, starch, dextrine, alkyl glucosides, albuminous materials,cellulose derivatives soluble in water October 7,1941, to White.

Other compounds susceptible to treatment with allyl glycidyl etherinclude phenols, substituted phenols, cyclic alcohols such as terpineol,tetra- 'hydrofurfuryl alcohol, hydrogenated phenols, etc.

Acids (either monocarboxy or polycarbox'y) can be reacted with thesereagents. Similarly, amines such as tertiary amines containing at leastone alkanol radical, or primary or secondary amines which contain anamino hydrogen atom and may or may not contain an alkanol radical, canbe used. This applies to polyamines as well as monoamines, mercaptans,such as decyl mercaptan, dodecyl mercaptan, etc.

Allyl glycidyl ether can be reacted with numerous other cellulosederivatives such as those described in U. S. Patents No. 2,033,126,2,135,128, 2,157,530, 2,055,893, and 2,136,296.

Obviously, the various materials previously described can be convertedinto derivatives having an amino radical or the number of amino radicalscan be increased by reaction with ethylene imine or propylene imine.

Needless to say, such allyl derivatives of the kind enumerated above andintended for use as in preparing a copolymerizable mixture withallylsucrose may be polymerized alone in absence of allylsucrose.Similarly, mixtures of the allyl compounds other than allylsucrose, maybe copolymerized to give suitable polymers. In any event, such polymersobtained, in the absence of allylsuorose, from one or more of the allylcompounds or similar allyl compounds can be oxyalkylated in the mannerdescribed subsequently in Part 3 so as to yield valuable oxyalkylationderivatives. The products so obtained are useful not only for thepurpose of resolving oilfield emulsions in the same manner as describedin Part 4 but also for other uses such as making emulsions or acting asan emulsion promoter or additive in conjunction with other emulsifyingagents. They may be used as deflocculating agents and also asintermediates for further reaction through the terminal hydroxylradical. In all such instances polymerization can be promoted byperoxide catalysts as well as by blowing. Allylsucrose, as is obvious inlight of what has been said previously, is used in two definite senses;one to mean a specific allylsucrose, for

instance, penta-allylsucrose specifically; and gen-- erically to meanany allylsucrose. or for that matter a cogeneric mixture of one or moreallylsucroses. However, this does not lead to confusion because thesense of the text in each instance is obvious.

As examples of suitable mixtures the following are included for purposeof illustration:

Example 10.

750 grams of allylsucrose (principally pentaallylsucrose) were mixedwith an equal part of diallyl glycerol. This mechanical mixture was usedsubsequently in the same manner as allylsucrose.

The above applies to subsequent examples in which no mor data will begiven other than mixture ratios as they are mechanical mixtures andnothing more.

Example 2a Sorbitol was reacted in presence of /2% of sodium methylatewith 4 moles of allyl glycidyl ether. 750 grams of this end product weremixed with 750 grams of allylsucrose (principally pentaallylsucrose)Example 30!.

Sorbitol was reacted with 6 moles of ethylene oxide and the resultantproduct reacted with 4 moles of allyl glycidyl ether. Oxyethylatedsorbitol is available commercially or can be prepared Pentaerythritolwas reacted with 4 moles of ethylene oxide and 'imole's of allylglycidyl ether.

750 grams of this material were mixed with 750 grams of allylsucr-ose(principally penta-allylsucrose).

Example 6a Triglycerol obtained by reacting 2 moles of glycide to onemole of glycerol was reacted with 3 moles of allyl glycidyl ether. 650grams of this product were mixed with 850 grams of allylsucrose(principally penta-allylsucrose).

Example 7a 150 .gramsof allyl oleate were mixed with 1350 grams ofallylsucrose (principally penta-allylsucrose) Example 8a Glycerolalpha-allyl ether is mixed with allylsucrose (principallypenta-allylsucrose) in the ratio of 1200 grams of allylsucrose and 300gram of glycerol alpha-allyl ether.

' Example 9a Triethanolarnine is treated with allyl glycidyl ether inthe ratio of 3 moles of the ether for one mole of the triethanolamine.300 grams of this material are mixed with. 1200 grams of allylsucrose(principally penta-allylsucrose).

Example 100.

1100 parts of allylsucrose (principally pentaallylsucrose) were mixedwith 200 parts-of diallyl glycerol and 200 parts of glycerol alpha-allylether. Example 1 1 a One mole of allyl alcohol was reacted with one moleof allyl glycidyl ether so as to produce a compound having two allylgroups and one'hydroxyl radical. 150 grams of this material were mixedwith 1150 grams of allylsucrose (principally penta-allylsucrose).

Example 12a 150 grams of allyl starch were mixed with 1150 grams ofallylsucrose (principally penta-allylsucrose). See IndustrialandEngineering Chemistry, volume 35, page 201 (1945).

Example 13a Allyl oleate was heated to 125 0., and blown with air for100 hours. At the end of this time the product had turned from'a paleyellow to an almost black viscous liquid and indications were thatfurther blowing would cause astringy polymer. 200 grams of this materialwere mixed with 1000 grams of allylsucrose (principally pen-taallylsucrose) Example 114a;

Allyl ricinoleatewas blown in the samemanner as mdic'a'ted in Example13a: preceding, except that blowing "was stopped at the endoff'8'ihours,

This particular product did notdisc'olor "and also approached just shortof the'strin'gy zstag'eiin'20 less time than in the case of the oleate.'250' grams of this product were mixed with 1250 grams of allyl'sucrose(principally penta-allylsucrose); j

Example 15a 7 7 An allyl naphthenatewas preparedirom alight colorednaphthenic acid obtained from California crude. The specifications onthisparticular naphthenic acid areas follows:

Acid number, oil-free" 247 Unsaponiflable content (percent by weight) '7Color (ASTM) 3 3 Water content"'(percent by weight) 0.3' Viscosity'atF.,S.S. U--. 3'00 Specific gravity, 60 F; 0.98

This particular allyl compound was blown for 87 hours .until just shortof the stringy stage. It disclosed only slightly. product were mixedwith 125,0v grams of allyl su crose (principally penta-allylsucrose) VExample 'lba 250 grams of glycerol alpha-allyl. ether monoallylsuoleatewere. mixed with 1250 grams of crose (principally penta-allylsucrose)Example 170.

250' grams of glycerolalpha-allyl ether monoricinoleate were mixed'with.1250 grains of allylsucrose, (principally penta-allylsucrose) Example:13811.1

.250 grams'of glycerol alpha-allylether mono naphthenate were mixed with1250 grams of allylsucrose (principally penta-allylsucrose) Thenaphthenic acidused to form the fractional ester was the particular onedescribed'under the heading of Example Ifia, preceding.

Example 1.9a

Diallyl phthalatewas blown until it became rubbery. The temperature ofblowing wash-215 C. The time required'was 19% hours.- The polymerizationwasthen repeated under identical conditions but pol'ymerizationstopped 9hours 'short'of this time; i. e., at the end of 10 hours. 250 grams of"the partially polymerized diallyl phthalate above described-"were mixedwith 1250 grams of 'allylsucrose (principally penta-allylsucros'e).

Example 20a Diallyl catechoLwas-blown for 453/ hours. At the end of thistime the product was a semi-rubbery mass. The temperature of blowing wasC. The process was repeated and the oxidizing stopped 8 hours short ofthe previous stage,.i. e., at the end-of 37 hours.

250 grams of this partially polymerized =diallylcatechol were mixed with.1250 grams of allylsucrose (principally penta-allylsucrose) 7 As to thepreparation of diallyl catechol, and diallyl 'resorcin see U. S.'P-atent'No. 2,459,835,, datedJanuary 25, 1949, to Monroe.

Needless to say, mixtures containing an allylsucrose need not be binarymixtures but can have three or more components, as, for'example, a mix;

250 grams of this blown PART 2 In regard to polymerization ofallylsucrose reference is made again to the aforementioned Zief andYanovsky article in Industrial and Engineering Chemistry.

The following table, data, etc., are in substantially verbatim form asthey appear therein:

POLYMERIZATION A previous article pointed out that for someapplications-for example, coating mate- 'rialsit is advisable to oxidizethe product partially to increase viscosity. Since, during this partialpolymerization, the refractive index increase parallels the increase inviscosity, by observing the change in refractive index and interruptingthe oxidation at a standard value, unipartially polymerized, has atendency to polymerize and eventually gel, even at room temperature. Itis important, therefore, to know how long the polymerized substance willbe kept before use. i

The effect of storage on monomeric and partially polymerized allylsucrose was investigated. Allylsucrose (6.7 allyl groups) waspolymerized at 100 C. At several points (Figure 1) 25-cc. samples werewithdrawn, put into glass vials closed with plastic screw caps, andstored on a laboratory shelf at room temperature (about 25 0.). Fromtime to time the index of refraction of each sample was examined. TableII gives the results.

Table II shows clearly that, whereas the a1lyl sucrose as prepared(sample 1) scarcely changed during a year of storage, the partiallypolymerized samples of refractive index 1.4920 or higher gelled atvarious intervals during this period; the sample of refractive index1.4911 closely approached the gelation point after 12-month storage.Although sample 7 gelled in about 4.months, 50% solutions of the samesamples in toluene and turpentine showed no sign of gelation after ayear of storage.

Sample No.

Refractive Index, m,"

10 weeks 18 weeks 26 weeks 8- 50% soln. of No. 7 in Turpentine.

Toluene Nichols, P. In, .Tr., and Yanovsky, Elias, Sugar, 42,

form results will be obtained. Figure 1 shows the viscosity andrefractive index curves for a laboratory batch of allylsucrose made withallyl bromide. Since laboratory preparations are fairly wellstandardized with regard to ally] content, viscosity, refractive index,and gelation time, reproducible results were obtained whenever thepartial polymerization was interrupted at the same refractive index.

Allylsucrose prepared in a glass-lined autoclave with allyl'chloride hasa lower allyl content than the products prepared with allyl bromide and,hence, gives different values for viscosity,

refractive index, and gelation time. The ViSCOs- -'The closer therefractive index is to the gelation point, the quicker will the film ofallylsucrose become tack-free on exposure to air. Thus a 50% solution ofallylsucrose in toluene or turpentine (having a refractive index of1.4940) with 0.1% of cobalt (as naphthenate or octoate) dried tackfreein 60 to 90 minutes at room temperature.

0n the other hand, allylsucrose, particularly when (Hereto attachedFigure 1 corresponds to Figure 1 in the text of the original article.)

The semi-commercial samples of allylsucrose available appear to containa small amount of volatile aromatic solvent. The actual blowingoperation appears to be checked until this bit of aromatic solvent hasbeen blow out. Such allylsucrose can, of course, be blown with orwithout agitation. Agitation in essence speeds up the polymerizationreaction for obvious reasons. It is in essence more vigorous blowingconveniently controlled. In the aforementioned Zief and Yanovsky articlereferred to in detail above it is, of course, obvious that theseinvestigators were interested perhaps primarily in obtaining a materialsuitable as a coating. This meant that the blowing operation might wellbe conducted with a view of preventing darkening and also with a view ofobtaining material which was still uniformly soluble in a solvent, suchas toluene or xylene. In the instant invention blown or polymerizedallylsucrose is nothing more than an intermediate for further reaction.Color or solubility of the kind which might be desirable in a coating isnot critical for the instant purpose.

Below are three typical examples in which various degrees ofpolymerization have been obtained by blowing. Allylsucrose orallylsucroses can be polymerized by peroxides such as benzoyl peroxide,in a conventional manner but the procedure is less satisfactory than airblowing. The

final resultant products are probably substantially identical provided,.of course,=thatthe pen oxide polymerization has not 'beenconducted soas to result in an insoluble compound or mixture. It is hardly necessaryto add to whathas appeared in the literature in regard to the art ofpolymerization by blowing of allylsucrose but the following examples areincluded for illustration and for the reason that cognizance has beentaken of .the fact that allylsucrose (approximately allyl groups on theaverage per sucrose molecule) is somewhat dispersible in water,.and alsosome- .what dispersible in the initial stage of polymerication. However,in the latter stage of oxidation orpolymerization this is not true as isillustrated by the subsequent examples. compounds can be polymerized inthe same man- 'ner employed to polymerize allyl esters. See'U. S. PatentNo. 2,374,081, dated April 1'7, 19%, to

'Dean. 7

Example 1b The allylsucrose was blown on a laboratory scale usingapproximately 1500 grams of allylsucrose in a 3-liter flask. Theterminal air inlet was provided with a device which gave a. multiplicityof small, fine bubles. The rate of airwas such that there was acontinuous istreamof air passing through the reaction mass sufficient toprovide at least moderate agitation. The data in the following table donot require explanation:

Tempera Time, :Min- :Indexof Be:- :5 tumL 0 Q. I gheg fraction Watersolubility 0 blspe sible. 9,0 25 Do, 95 D0,. 09 D0. 99 .0 D 135 Do. 95180 Do. 98 210 Do. 270 Do. 100 330 Do. 90 360 Do. 96 390 Do. 104 420Less dispersible. '100 440 Insoluble.

100 460 Do. 100 480 Do. 100 490 Do. 100 510 Do. 100 540 Do.

In the above experiment the change in refractive index after about 45minutes of blowing probably meant that all the solvent presenthad beeneliminated. Also, note that when the oxidation stage wh ch r quired abo9 h urs in ll,

was about eighty per cent complete the product no longer showeddispersibility comparable to the initial product or the early stages ofpolymerization. This product was considered as the result Qf mildblowing, or mild polymerization. See

,what said in regard to such characterization in the discussi n of the nxt exampl Example 21).

The same procedure was employed as in Example lb .except that a stirringdevice was inch ded along withthe distributing vent. In this instancethe temperature was held at C. tor three hours, at the end of whichtime, the prodnot still showed dispersibility. Itwas then :held

At theend of this.

at 100 for two more hours. time the product was not water-soluble andwas very stringy or even semi-rubbery. When diluted with, an equalweight of xylene the dilute solution was still very viscous and somewhatrubbery. The refractive index was 1.4985. Note that this is a higherfigure than is shown in the table re- These various allyl respect asinExample 2b except that the second stageoi oxidation at 100 C. waspermitted to take 12 ierred to the article by Zief and Ya'novsky. no?purpose of convenience in referring torblown all lylsucrose I have usedterminology somewhat comparable to that applied in regard to other blownproducts, such as blown .castor oils, I have considered a productwhichisblown toju'stshort I of the rubberystage and is exemplified by Ex-vample 1b, preceding, as mildly oxidized, mildly blown, or mildlypolymerized. I have used the expression drastic polymerization toindicate a product which is not only'stringy or rubbery as suchbut alsoisv highly viscous and shows stringiness or rubberiness fin a*50%xylene-sour.

I Example 312 V 7 V Thesame procedure was employed "in every place for 1/2 hours only instead of 2 hours, and the refractive index at the end ofthis time was 1.4980. The product showed a definite tendency to stringor rubberize but this property practical- 1y disappeared when a 50%solution in xylene was prepared. 7

Actually blowing or polymerizing can be conducted with ozone or ozonizedair as well as air which-may or ma not have its moisture contenteliminated. In this particular type of reaction I'have found no advantae in going to any added cost in regard'to the oxygenatin procedure whichinitiates pol merization. In the polymerization of com ounds in whichbasic amino radicals are present I prefer to use air which has beenstripped of carbon dioxide by means of sodalime or any oth r convenientmeans. V

The same is tr e of a catalyst, such as lead,

man anese or cobalt nanhthenate or the likeas I has been described inthe literature previoush mentioned. Such catalyst in comparati e y smallamounts. one-tenth per cent or preferably less, 7 will s eed up the polmerization but here a ain I have not found this particularly des rable.Since it is us ally intended to stop the polymerization at someparticular point by use of a mild blowing or a semi-drastic blowing. ora drastic blowin it is of greater convenience to a proach" the end pointslowly rather than rapidly. and also to have polymerization ceasewhemthe air stream stops.

Re erring again to the sucrose, as has been pointed out, one of theobjectives appears to be, concerned with a suitable coating material.Everything else being equal presumably the fewer hydroxyl radicalsavailable in the coating material the better. On the-other hand as anintermediate reactant this-need not apply. Sucrose as an initial rawmaterial hasv 8 hydroxyl radicals. Diallylsucrose, of course, would havean excess of hydroxyl radicals .over allyl radicals and would notpossibly be-particularly suitable for a coating material. This does notapply to its use as an intermediate as herein described. The same wouldbe true of triallyl- The product now sucrose or tetra-allylsucrose.available in at least pilot plant quantities and perhaps shortly incommercial quantities apdevelopment of allylallylsucrose present, withperhaps minor amounts 'or' almost insignificant amounts of otherallylsucroses. A Tetra-allylsucrose, in which the allyl radicals and thehydroxyl radicals are equal. is a particularly suitable reactant. Inpenta-allylsucrose and hexa-allylsucrose there are more allyl radicalsthan hydroxyl radicals. The effect of this variation in the molecule issignificant, par ticularly insofar that it "affects the molecular weightof the ultimate oxyalkylated product described subsequently in at leasttwo ways (a) The'more hydroxyl radicals the more long ether chains whichcan be added per molecule. (b) On the other hand the more allyl radicalsProbablythe larger the polymerized molecule although this maynct betrue. It may be better to assumethe more allyl radicals the more readilythe-product can be blown or polymerized." Excessive polymerizationeliminates solvent solubility. The product resulting from polymerizationmust meet this solubility test, and must also besusceptible tooxyalkylation in absence of a solvent and particularly oxyalkylation in'pre 'ence ofasolvent. A H

There is a fairly narrow range where the product ifgivensuper-drastictreatment is only partially soluble at the most in xyleneor the 'like'but is still soluble, at least sufiicient for the purpose,in aQ'semi-polar solvent such as dioxane, ethylene glycol' diethylether, diethylene glycol diethyl etherand tetraethylene glycol dimethylether. Q I 7 Other solvents include hydrogenated aromatic materials suchas tetralin and decalin, andethers containing an aromatic radical suchas p-tert- "amylphenyl methyl ether, p-tert-amylphenyl nbutyl ether,n-butyl phenyl ether, or more highly oxygenated solvents obtained bytreating benzyl alcohol or phenol or alkylated phenol'with 1, 2 or '3moles of an alkylene oxide, such as ethylene oxide or propylene oxide,followed by methylation so as to convert the terminal oxygen-linkedhydrogen atom into a methyl radical.

Stringiness or rubberin'ess as described above is probably an indicationof incipient cross-linking or gelation. In any event the allylsucrosesand particularly those having a plurality of allyl groups asdifferentiated from monallylsucrose, can be divided into three classes:(1) Thosein --which'there are more hydroxyl radicals than allylradicals, with (2) the number of hydroxyl radicals and allyl radicalsapproximately equal, and (3) 'where the number of allyl radicals aregreater cedure above described that higher polymers such as tetramers,pentamers, etc., are formed to a greater or lesser degree. However, atsome subsequent stage as soon as more than incipient cross-linking takesplace the polymers are no longer soluble in xylene or in some of thesemipolar solvents described, or in a mixture of the two. It is to benoted that the solvents of the semi-polar type are characterized by thefact that they may be present in the subsequent oxyalkylation step andare not susceptible tooxyalkylation. It is to be noted also that in thesubsequent description of the oxyalkylation step (Part 3) it becomesobvious that with a tetramer or pentamer and probably even in the caseof a trimer, one may readily obtain derivatives in which the molecularweights are in the neighborhood of -1000,000 or thereabouts.

Part 3 Numerous derivatives of the kind described in Part 2, preeding,have been prepared on a scale varying from a few hundred grams on alaboratory scale to larger amounts. This applies also to the preparationof oxyalkylated compounds of the kind or type comparable to those withwhich this third part of the text is concerned. In preparing a largenumber of examples I have found it particularly advantageous to uselaboratory equipment which permits continuous oxypropylation andoxyethylation. More specific reference will'be made to treatment withglycide, subsequently in the text. The oxypropylation step is, ofcourse, the same as the oxyethylation step insofar that two low boilingliquids are handled in each instance. What immediately follows refers tooxyethylation and it is understood that oxypropylation can be handledconveniently in exactly the same manner.

The oxyethylation procedure employed in the preparation of derivativesof the preceding intermediates has been uniformly the same, particularlyin light of the fact that a continuous operating procedure was employed.In this particular procedure the autoclave was a conventional autoclave,made of stainless steel and having a capacity of approximately onegallon. and a working pressure of 1,000 pounds gauge pressure. Theautoclave was equipped with the conventional devices and openings, suchas the variable stirrer operating at speeds from 50 R. P. M. to 500 R.P. M., thermometer well and thermocouple for mechanical thermometer;emptying outlet; pressure gauge, manual vent line; charge hole forinitial reactants; at lease one connection for conducting the incomingalkylene oxide, such as ethylene oxide, to the bottom of the autoclave;along withsuitable devices for both cooling and heating the autoclave,such as a cooling jacket and, preferably, coils in addition thereto,with the jacket so arranged that it is suitable for heating with steamor cooling with water, and further equipped with electrical heatingdevices. Such autoclaves are, of course, in essence small scale replicasof the usual conventional autoclave used in oxyalkylation procedures.

Continuous operation, or substantially continuous operation, is achievedby the use of a separate container to hold the alkylene oxide beingemployed, particularly ethylene oxide. The container consistsessentially of a laboratory bomb having a capacity of aboutone-halfgallon, or somewhat in excess thereof. This bomb was equipped, also,with an inlet for charging, and an outlet tube going to the bottom ofthe container so as to permit discharging of alkylene oxide in theliquid phase to the autoclave. Other conventional equipment consists, ofcourse, of the rupture disc, pressure gauge, sight feed glass,thermometer connection for nitrogen for pressuring bomb, etc. The bombwas placed on a scale during use and the connections between the bomband the autoclave were flexible stainless hose or tubing so thatcontinuous Weighings could be made without breaking or making anyconnections.

This: also applied to the. nitrogen line, which was useditopressure thebomb reservoir; To. the extent that it. was: required, any other usualconventional procedure or addition which provided greater'safety wasused, of course, such as safety glass, protective screens, etc;

With this particular arrangement practically all oxyethylations becomeuniform in that the reaction temperature could be held within 'a fewdegrees of any selected point in this particular range. In the earlystages where the concentration of catalyst. is highthe temperature wasgenerally set for around 150 C. or thereabouts. Subsequentlytemperatures up to 170 0.. or higher may be required It will be noted byexamination of subsequent examples that this temperature range wassatisfactory. In any case, where the reaction goes more slowly a highertemperature may be used, for instance, 165 C. to 180 C., and if need be185 C. to. 190 C. Incidentally, oxypropy-lation takes place more slowlythan oxyethylation as a rule and for this reason we have used. atemperature of approximately 160 C. to 165 C., as being particularlydesirable for initial oxypropylation, and have stayed within the rangeof 165 C. to 185 (3., almost invariably during oxypropylation. Theethylene oxide was forced in by means of nitrogen pressure as rapidly asit. was absorbed. as indicated by the pressure gauge on. the autoclave.In case. the reaction slowed up the temperature was raised so as tospeed up the reaction somewhat by use of. extreme heat. If need be,cooling water was employed to control the temperature.

As previously pointed out. in the: case. of oxypropylation asdifferentiated from oxyethylation, there was a tendency for the reactionto slow up as the temperaturedropped much below the selected point ofreaction, for instance, 170 C. In this instance the technique employedwas the same as before, that is, either cooling waterwas cut down orsteam was employed, or the addition of propylene oxide speeded up, orelectric heat used in addition to the steam in order that the reactionproceeded at, or near, the selected temperatures to be maintained.Inversely, if the reaction proceeded too fast regardless of theparticular alkylene oxide, the amount of reactant being added, such'asethylene oxide, was cut down or electrical heat was cut off, or steamwas reduced, or if need be, cooling water was run through both thejacket and the cooling coil. All these operations, of course, aredependent on the required number of conventional gauges, check valves,etc., and the entire equipment, as has been pointed out, is conventionaland, as far as we are aware, can be furnished by at least two firms whospecialize in the manufacture of this kind of equipment.

Attention is directed to the fact that the use ofglycide requiresextreme caution. This is particularly true on any scale other than smalllaboratory orsemi-pilot plant operations. Purely from the standpoint ofsafety in the handling of glycide, attention is directed to thefollowing; (a) If prepared from glycerol monochlorohydrin, this productshould be comparatively pure; (1)) the glycide itself should beas pureas possible as the effect of impurities is diflicult to evaluate; (c)the glycide should be introduced carefully and precaution should betaken that it reacts as promptly as introduced, i. e., that no excess ofglycide is allowed to accumulate; (d) all necessary precaution should betaken that glycide cannot polymerize per se; (e) due to the high boil-16 ing. point of glycide: one; cam-readily" emplcy -a typicalseparatable glass resin pot asdescribed-in U. S,Patent. No.2,499,370;dated March 7-, I950;

and offered for sale. by numerous laboratory supply houses.

If such. arrangement is used to prepare laboratory scale duplications,then care should betaken that the heating mantle can be removed rapidlys0= astoallow for cooling; or better still, through: an added opening atthe top the glass resin pot or comparable vessel-should be equipped witha stainless steel cooling coilso that the pot can be cooledmore rapidlythan mere removal of mantle. If a stainless steel coil is introduced itmeans that conventional stirrer of the paddletype is changed into thecentrifugal type which causes' the fluid or react- I ants to mix duetoswirling action in the centerof the pot. Still better, is the-use ofa'laboratory autoclave of the kind previously described in this part;but in any event, when the initial amount of glycide is added to asuitable reactant,-such as apolymerizedallylsucrose or'a polymer deriveda from anallylsucrose mixture, the speed of reac tion should becontrolled by the usual factors, such as (a)- the addition of glycide;(b) the elimination of external heat, and (0) use of coolingcoilso'there is no undue rise in temperature. All

the foregoing is merely conventional but is ineluded dueto the hazardinhandling glycide.

As has been pointed out previously oxyalkyla tioninvolving the use ofallyl glycidyl ether is conductedin a manner similar toglycide, a1 Ithough inthe main this: latter reactant-aonearsat times to be morereactive and if in doubt as to the suitability of any particular euipment or.

procedure it should be cautiously ex lored before adoption, either on alaboratory scale, ilot plant scale, 01' large scale. Reactions involvingglvcide probably takes place more ra idly and at lower temperature thanallvl glycidyl ether; for in.-

stance, at to C. If the reaction does not take place at thistemperature, the temperature should be increased sli htly, andparticularly slowly and cautiously. If the reaction does. take placeat'this temperature and starts to proceed too rapidly it should becontrolled carefully. Briefly, the'lowest temperature'of reaction shouldbe employed which is consistent with uniform and constant reactionwithout a tendency either of pro ylene oxide or butylene oxide as asolvent as well as a-reactant in the earlier sta es along with ethyleneoxide,for instance, by" dissolving the appropriate resin propylene oxideeven though oxyalkylation is taking place to a reater or lesser degree.After'a solution has been obtainedv which represents the selected resindissolved in propylene oxide or 'butylene omde, or a mixture which.includes the oxyalkylated product, ethylene oxide is added to react withthe liquid mass until hydrophile properties are obtained. Since ethyleneoxide is more reactive than propylene oxide or butylene oxide, the finalproduct may contain some unreacted propylene and Engineering Chemistry,volume 42, No. 6, June 1950, pp. 1251-1258.

Example h d Grams TBl'own allyl sucrose identified as Example 3bpreceding 421 Ethylene oxide 990 Xylene 421 Sodium methylate 10 I Theabove mixture was placed in an autoclave and adjustment made so that thetemperature .wouldvary between 180 to 200 C. The pres- ;sure control wasset so that the pressure would .notgo above 190 p. s. 1. during theoperation.

Blown allylsoucrose (same as Example 10 above) 419 Xylene 419 .Sodiummethylate 10 Propylene oxide 1205 In this instance the automaticapparatus was set so that the propylene oxide was introduced "in a twoand one-half hour period and an additional half hour added forcompletion of reaction. The temperature range was set between 165 and180 C. The maximum temperature actually reached was 175 C. The pressureregulator was set for 160 p. s. i. maximum. The highest pressurereached, however, was only 150 p. s. i.

' The composition so obtained on a xylene-free ,and xylene-containingbasis is as follows:

Per Per cent cent Blown allyl sucrose 25.6 20.5 Propylene oxide 74.459.0 Xylene 20.5

The product was xylene soluble and water insoluble.

Example 30 1,231 grams of the product identified as 10 preceding andrepresenting 283 grams of blown allyl sucrose, 283 grams of xylene and665 grams of ethylene oxide was treated in the same manner as beforewith an additional 370 grams of ethylene oxide. During this operation,the automatic equipment was set for a maximum temperature of 200 C., amaximum pressure of 200 p. s. i. and for a reaction time of 30 minuteswith Na subsequent stirring period of another 30 minutes. .arployedn Attheend of the reaction the composi- No additional sodium methylate wasemcomposition in terms of the reactants was as fol- 7 lows:

' Per Per cent cent Blown allyl sucrose 29.9 23.0 Ethylene oxide 70.154.0 Xylene 23.0 The product was xylene soluble and water emulsifiable.

Example 20 Grams 18 tion on'both the xylene-free and xylene-contain ingbasis was as follows;

Per Per cent cent Blown allyl sucrose 21.5 17.7 Ethylene oxide u 78564.6 Xylene e r 17.7

The product was xylene soluble and water soluble.

Example 40V 1,070 grams of the product identified as 3c preceding andrepresenting 191 grams of blown allyl sucrose, 191'grams of xylene and698 grams of ethylene oxide were treated with 995 grams of propyleneoxide. 10 grams of sodium methylate were added asa catalyst. Theautomatic equipment was set for a maximum temperature of 200 C. and amaximum pressure of 165 p. s. i. The maximum pressure reached during thereaction, however, was only 150 p. s. i. The equipment was set tointroduce the propylene oxide in one hour with a subsequent stirringperiod .of onehalf hour. The reaction could have been completed inconsiderablyless time due to the added catalyst. The composition of .theproduct on both a xylene-free and a xylene-containing basis is asfollows:

Per Per cent cent Blown allyl sucrose' 10.1 9.2 Ethylene oxide 37.1133.7 Propylene oxide 52.8 47.9 Xylene 9.2

The product was both water soluble and xylene soluble.

" "Example 957 grams of the product identified as 2c preceding andrepresenting 196 grams of blown allyl sucrose, 565 grams of propyleneoxide, and 196 grams of xylene was mixed with an additional 10 grams ofsodium methylate and then reacted with an additional 1355'. grams ofpropylene oxide. The automatic process equipment was set never got above100 p. s. i. The composition of containing basis is "as follows:

the product both on a xylene-free and a xylene- Per Per cent cent Blownallyl sucrose 9.2 8.5 Propylene oxide 90.8 83.0 Xylene 8.5

The product was xylene soluble and water insoluble.

Example 60 600 grams of a product previously identified as 2c precedingrepresenting 123 grams of blown allyl sucrose, 354 gramsofpropyleneoxide and .123 grams of xylene was mixedwith 5 grams of mentdid not function properly and actually a maximum pressure 01230 p. s. i.was'reached.

2,574,544 wiser-.3: 4w: .5: a. 4.0 as; 1 .4. The composition of thepresses on hot axylene- The product was dispersible in water and so nfree and xylene-containing basis was as follows:

' i?! Per fBlijwn allyl sucrose Propylene oxide ---Ethylene oxide. e e50.7 Xylene The product was soluble in both xylene and I water.

L197 'gramss:of the lproduct identified as .40

iandrepres'enting morsgrams ofsallyl sucrose,':403

'grams-of ethylene: oxide;:'-574 gramsxof propylene oxide and llo'g-ra-ms of xylene was mixed with grams of sodium methylatetandtheni'reacted with 13335 grams or propylene oxidez i The equipment wassetifor' a reaction period of onerhourcfollowed by thirty minutes =of'gstirringa The automatic "devices-were setfiforva maximum temperatureof 175" C. and a maxim-um'vpressure of "'5:p.' -s .:ai. The maximumpressure reached; however; .was

-only-11'0 p; s: i: "The composition ofsthe :product" 3 ou 'bothaxylene-free and xylene-containingbasis is as follows:

' Per I cent .Blbwn allyl sucrose 4.25 ffEthylene'oxide 16.6 16.0"Propylene'oxide 7&9 7525 Xylene;5.4;; 4 .25

The product was emulsifiable in water and,

xylene soluble. H M um... .1 NJ

666 grams of the pr odugt identified as 50 preceding representing 56.5grams of blown allyl sucrose; :553 g'rams oi Tnecem- "Xylene-free anda-xylene containing-basis is as -followsq The product was soluble inboth water and ze Example 99 on the xylene-free andxylene-containingbasis as fset for a' ma unfuntefixbrtfim of 1359.

ble in xylene. av .4:

Example 100 1,075 grams of propylene oxide.e.,l'lhe. reaction time wasset for an hour and one-half 'and tlie "stirring-period for anadditional hal f hour; '--'-1he equipmenu was set for a 'maximumaemperture of 185 C. and a maximum pressure of 2ilo pi s'i i. Actually, thepressurenever'reached higher :than 150-p. s. i. and'the reaction 'couldhaveibeen 15 *completedin less than an hourgpossiblwas little as a halfhour. The 'compositionyof the product "on 'both a xylene-free andxylene-containing basis is as follows:

'iPer 20... a Y 1 cent Blown allyl'sucrose .4;2

Propylene oxide Xylene The mate is j ust barelydispersible in' water,

perhaps better characterized as being insoluble but was soluble inxylene.

i 713 gramsofth'e product'identified as-lOc-p eceding representing 28.5-"grams of" blown "*allyl sucrose, 656 grams of;,tpropy-lenei; oxide; and$28.5

dium methylate and reacted with 475 grams of procedure could have beencompleted in one-half or one-third of the time indicatedg'flI'hecom- Vpo'sition of the materiallxboth omaixmene-rr e and a xylene-containingbasis'is as i llows:

- Blown'allyl I Propylene oxide v' Ethylene .oxide 7 j EP'EH' 'ITP'CTF-ETTKTJ'W'ITI M :j, H The product was soluble in both xylene and inwater. 7 V V a: Example 12c 758 "grams "of the product {identifled- 'asi 10c preceding representing -30-.5-gramsbf blownallyl sucrose,697-grams' (if-propyleneoxide mid -30.5 V

--:-grams of xylene iwasemi-xed with .5E-grams ;of sodium methylate' andtreated with 555 -gramszof propylene oxide. The equipment was-set for areaction period o'fgeigh't' 'hours followed by two "hours stirring onthe following day... The temperature was. setafor a" maximum 0'f'l80.fC..but in this instance did not reach inore.thanflTI'OfiiC.

Thejpressure device-was set for a maxiniumhf 200 p. s; i.-but failed toact properly-.andithe ppressure actually reached. 250 p. s. i.Thejcom-rr position of the .product. on; both.a..xylenefree V and axylene-containing basis isas f ollows" i Per Per H e r i ce'nt cent'Blown allyl sucrose 1 I 2.4

'Propyleneoxide l Xylene V 985grams of the mixtureidentifiedras 5 c. +p,.E ceding representing 83.5 grams ..of -lolown un grams of xylene wasmixed with 5 g rams;o;f.so-

ethylene oxide. The equipment was set for a.

. p.. s. i. and the. reaction .was so fasta-ithe awe-.544

inqayariety of ways, such as (a) first adding all the ethylene oxide andthen the propylene oxide, or (b) adding the propylene oxide and then theethylene oxide, or adding arnixtureofthe two oxides in a single step. Ineach instance xylene was present as a solvent but other suitablesolvents such as decalin, xylene or the like, couldbe used. Sodiummethylate was used as a catalyst in each instance but any other catalystwould be just as satisfactory. The amount of catalyst added in theinitial stage was equivalent, roughly, to 2% of the blown allylsucroseIn the final steps if the percentage dropped much below to sufficientsodium methylate was added to bring the amount oflcatalyst at the end ofthe reacttion up to 'l'lie1so1ubility of the products varied, as noted,

frorn xylene solubility, or for that matter solu-H bility in no-aromatickerosene, to a stage where the, product was completely soluble in waterand foamed in water on shaking.

In all these instances the operating conditionswere substantially .thesame as far as temperature and pressure goes, i. e., oxyalkylationtemperature of 150 to 200 C. and slightly in excess thereof, and amaximum operating pressure of 150 pounds per square inch up to 220 or225 pounds per square inch; In some instances'the reactions took placewith even less pressure, i. e., less than 150 pounds per square inch andrarely' gotslightly higher.

1 Operation was about the same in all instances, 1. e., the equipmentwas set usually so as to inject anywhere from l00 to 200 grams of anoxide, up to akilogram, per hour. The rate of stirring was about thesame, whatever was indicated as con venient, usually running from 150 R.P. M. up to r 4 50,135. P. M. Reactions, of course, could be speeded upin every instance by increasing the amount of catalyst; increased speedof reaction meant that reaction would take place in less time,

or at a lower temperature, or at less pressure, or

comparableconditions. As a matter of fact, using a longer period of timeand an increased amount cicatalyst oxyalkylations could be conductedat atemperature a proximately that of the boiling point of water, forinstance 95 to 115 C., with,

practically no pressure at all, or in any event at,

colored viscous liquids. This appearance waso'n.

asolventefree'basis.

' Composition on Solvent-tree Basis,

Allyls Percentage by Weight Compound Ex. N o.

Qxyalkylated Compound Ethylene Propylene Gra'ms esssassseassesseseassessusing other alkylene oxides, particularly glycide," thexprocedure wasmuch the same ex.- cept that'the treatment with glycide generallyinvolved the use of a glass reaction vessel as previously described. Byand largethe efiect of glycide-was. about the same as adding a somewhatsmaller amount of ethylene oxide. Stated another way, if a product weretreated with propylene. oxide'and then with a small amount of ethyleneoxide substantially the same results couldbe obtained by adding asomewhat decreased amount of glycide instead of ethylene. oxide;This-was true when the glycide was usedalso. However, different resultswere obtained apparently when. glycide was added at an earlier stage forthe reason that branching was involved. Thiscan be illustrated by thefollowing: Ifgthreemoles of penta-allylsucrose are polymerized. to.form. a trimer, this trimer presumably has approximately 9 hydroxyls ora few less. If this product were treated with l to 9 moles of glycidethere are then available an increased numberof hydroxyl radicals and maybe as many as, twice the original number. Such product, if subjected tooxypropylation or oxyethylation or both. yields a molecule which shows agreater branching or a greater branched structure.

The same would apply if the trimer were first treated with ethyleneoxide and then with glycide and propylene oxide, or with propylene oxideand with glycide and then with ethylene oxide. However. since the mostsuitable compounds were obtained without the use of glycide and usingthe cheaper alkylene oxides, to wit, ethylene oxideeandproylene oxide,this phase does not require further elaboration.

, In order ;to show the variety of materials obtainable by either theuse of propylene oxide or ethylene oxide, or a combination of the two,reference is made to the hereto attached draw,- ings, i. e., Figures 2and 3. In Figure 2 there is a trapezoidal, area indicated by thenumerals i, 2,-3and 4, which shows the composition of materials derivedsolely from blown allylsucrose as previously described, i. e., thematerial which is mostly, -,p.enta-allylsucrose. These particularcompositions were efiective demulsifiers on a number of oils tested in.the Gulf Coast area.

Reference is made to Figure 3 which shows an'umber ofcompositionsderived not only from blown allylsucrose but also from mixtures-came,

' kind-previously described.- These mixtures were},

particularly effective as demulsifierszori a ;im;m-: her ofCaliforniaoils. H'ff W "rely, asidejrom whatisisa'id' herein, refer, n; $;m de.fim mend nsapnliqaticn. Serial; No, 1fl6,483, filed February 27, 1950, infwhich I,- havoreferred to an invention within an invention,

I to Wit, a drawing showing a,sma ll area essena w w have been made, notonly from such iproducts as represented by Examples 2b, Vanda3b,preceding but also from products obtained byqfthe polylneria zation' ofmixtures, such'as mixtures of thelkingi, exemplified by Examples 2a, 4a,and 5a. Such mixtures, as previously pointed out,. cambe subjected topolymerization to yield polymerizedma; ter'ials comparable toExamplestll.'2b anda3br Such polymers derived from mixtures; oil-allycompounds. are just as satisfactory as" far asthe'. oxyalkylation stepgoes. as the polymers deriveda solely from 'allylsucrose. Thevariousapointson the drawingirefer to and illustrate such particlelarderivatives as w'ellaas those derivedzfmmmolya; merized allylsucroseonly As has been pointed out previouslyoxyalltylw tions andparticularly.oxyethylations',and olgys propylationsare conducted in awideivairiety ioif conditions, not only in regard to presenceoraloesence of cata1yst,'kind of catalystpreviously de-s scribed, but alsoin. regard to the time of reactionp temperature of reaction, speed'ofreactionnpresa sure during reaction, etc. For instance voxttafkylationscan be'conducted. at temperatures-Lu to approximately 200 C; withDIQSS-UIES miSbQUii-i the samerange up to about 200 pounds pe1fisqharinch. They can be conducted also .at t'empe' tures' approximatingthe-boilingpoin ofi wo te or slightly above, as for example l'lifi IUnder such circumstances thepressure wil'labej less than pounds persquare inch unless sc'm'a special procedure isemployed'as'is-sometimesithe case, to. wit, keeping" an atmosphere" ofin'ei'rii as such-.as nitrogen in the vessel du'r'inggf the" tion.Such-low temperature lowireacti" i oxypfopylations have beenidescribedi'ver plelily in U. S.Pa'fZGIIi'rIVOt 214 48 634 (fo l-I; F. et 'aL, datedSeptember 7,-19483' Ldwtemp'er i1 10w" pressure oxyprcpylations areparticular s'irable where the compound pang subjected: to

oxypropylation contains" one; two or'tfir'e e-points of re'actio'n only,glycols'and triols. A I v a The same procedure can" be employed-impoly'hydroxyla'ted materials of the kindherein; at;

scribed;- 'Prob'ably less byproducts ar formed? but 'the economy of theprocedure must beicon such as mon'oh ydric sidered; itegia much ereaterilengtlr ofractibxi? time: r v t v --'Si'n'ce low pressure, lowtemperature; speed oxypropylations require donsiderablet'tlmeit, forinstance, 1 tofldaysof'i hours ejacitatolconr i pleterxthe reaction,.the'y are cdnducted'ias; w vuler propylglycidyl ether. In anyevent',-.-howeve an such reactantscoritain the reactive ethylenewhethen...on; a' lahoratoryascales pilot plantmcale,

. noi'da-control-led valve which.snuts'emtrieipspyx; V

eneroxide: in event that the temperate; outsidma predetermined and setran e, stance, ,1'1 0"-; -to or, and-4b anoth valvewhich-shirts ofithepropylene; ox de tha matter eth-ylene oxide if it -is? ein ir the,pressuregets beyond a: premtemnnem rangje',.si1'ch-a 25t35-pouridslequipment is substantially t ame -as ismdniy empi oyed-forthispurpose-where-theuse 1 Y sure of reaction is niuch shoi'ter;- mysu'chfi'n a stances such automatic bdl ltl'bl s area not sarily used. I

Thus' alt ough 'the-varipusyexafiiples rev:

1y;.noted have been prepared -fat-compereiti high temperaturesandressures I havepr'e'par a;,;fe wfl;at low"pre's sures using1aboratoifyf--eq ment whichds designed to permitcontihuous ox alklationjwhether it'fbe oxypropylatioh -or'b I fInfa genera? way I have: started*out'swit hre iw v mesa n u gher temperatures were employe menr asssih tme a t a to t i qsx slons at 1 filial; P duct e e, ad more xre iicl lrtalyst." in mo t ta ics -tr m i1 /2.%' as cdmpa witu /z '011 less inhiguer-te'n oeracu're p1;

ad If the re enc 9f n inc eased amount ft lta stat hee d oi t e. Q Q 'Sable, naturally this is another'objection to; u

the low tem rat reand 1ong'reacti'on"-time 510;; a a V cedurei lt-issometimes'a-nui'sance-and expense to remove suchexcessive monster-Mmline: catalyst r Attention is directed to the fact'that-a; number cfithe heretoaattached claims are-characterized byuthe facttha't. there isthe added: provisoithat, the hydrophile 1,1)1QDBI'1318S ofsaidoxyalkylated derivative; in an equal weight,- of xylene-are sufliaclsptt PIFQQHQQ an -e he Said le V soluti shaken vigorously with onesesame blems tot ate a a a As has been pointed out preyiously, .tlieret. yide yariety of suitable polymers which oambe sujij ected i tooxyalkyllation by one s or 1 more or theiryiene oxides specifieu orby a;mixture oi the? m. atewith ethylene oxide; andthen finish propylene,oxide} 7 Previous exjanjme'sgilliist 9b luren I slp ieined a suableailyl ucroseoria SfiFrQf e mixt re, pol mer of the} kind described;

su allylsuc'rose polymer is subjected to tr'eats merit with a low molalreactive: alpha-5&8 ol'efi n' OXide'fSO as to render'the'productdistirictly'; hydrcphile in-nature as indicated by the fact" thatit becomes self emulsifi-able or miscible'fof soluble:- in; water',"=orself-dispersible; or

emulsifying properties? The? -e1'efin -exiues eme ployed-arecharacterized by the fact that they:

contain not over 4 carbon atoms and"ar'eselected from" the classconsisting-10f ethylene ox de; propylene oxide, butyleneoxide;.glycide'; and methyl glycidyletherfethyl g-ly'cidyl ether-and ide ringand may; behest considered as deriviti-vfek i ofwrs substituted ethylene.oxi'd'es.. I T116 solubils izing effect of the oxide'is d recu v mp mmfe1 Eoninstancqonelmight artially xya1kyI-- the desired propertypractical. they may produce marginally satisfactory depropylene oxide.

,trations of 0.5% to 5.0%. generallymore soluble in cold water than warmto the percentage of oxygen present, or specifically, to theoxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. .In glycide, it is2:3; and in methyl glycide 1:2. In such compounds the ratio is veryfavorable to the production of hydrophile or surfaceactive properties.However, the ratio, in propylene oxide, is 1:3, and in butylene oxide,1:4. Obviously, such latter two reactants are satisfactorily employedonly when the allylsucrose composition is such as to make incorporationof In other cases,

rivatives, or even unsatisfactory derivitives. They are usable inconjunction with the three more favorable alkylene oxides in all cases.-For instance, after one or several propylene oxide or 'butylene oxidemolecules have been attached to the allylsucrose polymer, oxyalkylationmay be satisfactorily continued using the more favorable -members of theclass, to produce the desired hydrophile product. Used alone, these tworeagents may in some cases fail to produce sufficient-ly hydrophilederivitives because of their relatively low oxygen-carbon ratios.

Thus, ethylene oxide is much more effective than propylene oxide, andpropylene oxide is more eifective than butylene oxide. Hydroxypropyleneoxide (glycide) is more effective than Similarly, hydroxy butylene oxide(methyl glycide) is more effective than butylene oxide. Since ethyleneoxide is the cheapest alkylene oxide available and is reactive, its useis definitely advantageous, and especially in light of its high oxygencontent. Propylene oxide is less reactive than ethylene oxide, andbutlyene oxide is definitely less reactive than propylene oxide.

' Considerable of what is said immediately hereinafter is concerned withthe ability to vary the' as one goes from minimum hydrophile property toultimate maximum hydrophile property.

In a general way approximate minimum hydrophile property may bedetermined by solubility. Such minimum hydrophile property orsubsurface-activity or minimum surface-activity means that the productshows at least emulsifying properties or self-dispersion in cold or evenin warm distilled water (15 to 40 C.) in concen- These materials. are

water, and may even be very insoluble in boil'mg water. Moderately hightemperatures aid in retiming the viscosity of the solute underexamination. Sometimes if one continues to shake a hot solution, eventhough cloudy or containing an insoluble phase, one finds that solutiontakes place to give a homogeneous phase as the mixture cools. Suchself-dispersion tests are conducted .in the absence of an insolublesolvent.

In a number of instances one can determine the fact that one is past theminimum hydrophile-hydrophobe balance, or at least in an opti- -mum zoneeven though one does not obtain a sol as described immediatelypreceding, by the fact that thehydrophile character is indicated by theproduction of an emulsion. For instance, one can :prepare an emulsionthat contains an inert sol-- vent such .as xylene to the extent of to50%.

Allthat one need to do is to have a xylene solu- 26 tion within therange of 50 to parts by weight of oxyalkylated derivatives and 50 to 10parts by weight of xylene and mix such solution with one, two or threetimes its volume of distilled water and shake vigorously so as to obtainan emulsion which may be of the oil-in-water type or the water-in-oiltype (usually the former), but, in any event, is due to thehydrophile-hydrophobe balance of the oxyalkylated derivative. I prefersimply to use the xylene diluted derivatives, which are describedelsewhere, for this test rather than evaporate the solvent and employany more elaborate tests, if the solubility is not suflicient to permitthe simple sol test in water previously noted.

If the product is not readily Water soluble'it may be dissolved in ethylor methyl alcohol, ethylene glycol diethylether, or diethylene glycoldiethylether, with a little acetone added if required, making a ratherconcentrated solution, for instance 40% to 50%, and then adding enoughof the concentrated alcoholic or equivalent solution to give thepreviously suggested 0.5% to 5.0% strength solution. If the product isself-dispersing (i. e., if the oxyalkylated product is a liquid or aliquid solution self-emulsifiable), such sol or dispersion is referredto as at least semi-stable in the sense that sols, emulsions, ordispersions prepared are relatively stable, if they remain at least forsome period of time, for instance'30 minutes to 2 hours, before showingany marked separation. Such tests are conducted at room temperature (22C.). Needless to say, a'test can'be made in presence of aninsolublesolvent such as 5% to 15% of xylene, as noted in previousexamples. If such mixture, i. e., containing a waterinsoluble solvent,is at least semi-stable, obviously the solvent-free product would beeven more so. Surface-activity representing an advancedhydrophile-hydrophobe balance can also be determined by the use ofconventional measurements hereinafter described. -One outstandingcharacteristic property indicating surfaceactivity in a material is theability to form a permanent foam in dilute aqueous solution, forexample, less than 0.5%, when in the higher oxyalkylated stage, and toform an emulsion in'the lower and intermediate stages of oxyalkylation.

Allowance must be made for the presence of a solvent in the finalproduct in relation to the hydrophile properties of the final product.The principle involved in the manufacture of the herein specifiedcompounds for use as demul'sifying agents, or for other uses, is basedon the conversion of a hydrophobe or non-hydrophile compound or mixtureof compounds into products which are distinctly hydrophile at least tothe extent that they have emulsifying properties or areself-emulsifying; that is, when shaken with water they produce stableor'semi-stable suspensions, or, in the presence of a water-insolublesolvent, such as xylene, anemulsion. In demulsification, it is sometimespreferable to use a prod-- uct having markedly enhanced hydrophileproperties over and above the initial stage of selfemulsifiability,although I have found that with products of the type used herein, mosteflicacious results are obtained with products which do not havehydroprile properties beyond the stage of self -dispersibility.

More highly oxyalkylated allylsucrose polymers give colloidal solutionsor sols which show typical properties comparable to ordinarysurface-active agents. Such conventional surface-activity may bemeasured bydetermining the surface'tension However, since such redor 1to 50,000 as in desalting practicefsuch an apparent insolubility in oiland water is not significant because said reagents undoubtedlyhave 1solubility within such concentrations. This same fact is true in regardto the material or materials employed a the demulsifying agent of myprocess.

In practicing my process for resolving petroleum emulsions of thewater-in-oil type, a treating agent or demulsifying agent of the kindabove described is brought into contact with or caused to act upon theemulsion to be treated, in any of the various apparatus nowgenerally'used to resolve or break petroleum emulsions with a chemicalreagent, the above procedure being used I alone'or in combinationwith'otherdemulsify ing procedure, such as the electrical dehydrationprocess.

One type of procedure is to accumulate a volume of emulsified oil in atank and conduct a batch treatment type of demulsification procedure to'recover clean oil. In this procedure the emulsion fis-admixed with thedemulsifier, for example by agitating the tank of emulsion and slowlydripping demulsifier into the emulsion. In some cases mixing is achievedby heating the emulsion while dripping in the demulsifier, dependingupon the convection currents in the emulsion to produce satisfactoryadmixture. In a third modification of this type of treatment, acirculating pump withdraws emulsion from, c. 'g., the bottom of thetank, and re-introduces it into the top of .the tank, the demulsifierbeing added, for example, at the suction side of said circulating pump.

In a second type of treating procedure, the

.demulsifier is introduced into the well fluids at the well-head or atsome point between the wellhead and the final oil storage tank, by meansof wise be incorporated in any of the treating procedures describedherein.

A third type of application (down-the-hole) of demulsifier to emulsionis to introduce the demul- -sifier either periodically or continuouslyin diluted or undiluted form into the well and to allow it "to come tothe surface with the well fluids, and

then to flow the chemicalized emulsion through any desirable surfaceequipment, such as employed in the other treating procedures. Thisparticular type of application is decidedly useful when the demulsifieris used in connection with acidification of calcareous oil-bearingstrata,

especially'if suspended in or dissolved in the acid employed foracidification.

In all cases, it will be apparent from the foregoing description, thebroad process consists simply in introducing a relatively smallproportion of demulsifier into a relatively large proportion ofemulsion, admixing the chemical and emulsion either through natural flowor through special apparatus, with or without the application of heat,and allowingthe mixture to stand quiescent naphthalene monosulfonicacid, 24%;

' 30 until the undesirable water content of the emulsion separates'andsettles from the mass.

The following is a typical installation. A reservoir to hold thedemulsifier of the kind described (diluted or undiluted) is placed atthe well-head where the effiuent liquids leave the well. This reservoiror container, which may vary from 5 gallons to 50 gallons forconvenience, is connected to a proportioning pump which'injects thedemulsifier drop-wise into the fluids leaving the well. Suchchemicalized fluids pass through the flowline into a settling tank. Thesettling tank consists of a tank of any convenient size, for instance,one which will hold amounts of fluid produced in 4 to 24 hours (500barrels to 2000 barrels capacity), and in which there is a perpendicularconduit from the top of the tank to almost the very bottom so as topermit the iricoming fluids to pass from the top of the settling tank tothe bottom, so that such incoming fluids do not disturb Stratificationwhich takes'place during the course of demulsification. The settlingtank has two outlets, one being below the water level to drain off thewater resulting from demulsification or accompanying the emulsion asfree water, the other being an oil outlet at the top to permit thepassage of dehydrated oil to a second tank, being a storage tank, whichholds pipeline or dehydrated oil. If desired, the con-' duit or pipewhich serves to carry the fluids from the well to the settling tank mayinclude a section of pipe with bafiles to serve as a mixer, to insurethorough distribution of the demulsifier throughout the fluids, or.aheater for raising the temperature of the fluids to some convenienttemperature, for instance, 120 to 160 F., or both heater and mixer.

Demulsification procedure is started by simply setting the pump so as tofeed a comparatively large ratio of demulsifier, for instance, 125,000.As soon as a complete break or satisfactory demulsification is obtained,the pump is regulated until experience shows that the amount of de--mulsifier being added is just sufficient to produce clean or dehydratedoil. The amount being fed at such stage is usually 1:10,000, 1215,000,1:20,000, or the like.

In many instances the oxyalkylated products herein specified asdemulsifiers can be conveniently used without dilution. However, aspreviously noted, they may be diluted as desired with any suitablesolvent. For instance, an excellent demulsifier can be obtained bymixing 15 parts by weight of xylene and 10 parts by weight of isopropylalcohol with parts by weight of an oxyalkylated derivative, for example,a product obtained by treating a polymerized allylsucrose identified asExample 2?), preceding, with ethylene ovide and then with propyleneoxide, so that the derivative, assuming completeness of reaction,represents 5% blown allylcucrose, 15% ethylene oxide and propyleneoxide. Selection of the solvent will vary, depending upon the solubilitycharacteristics of the oxyalkylated product and, of course, will bedictated in pa by economic considerations, i. e., cost. 1 I

As noted above, the products herein described may be used not only indiluted form but also may be used admixed with some other chemicaldemulsifier, for instance, a mixture comprising the following:

Oxyalkylated derivative as described in the paragraph immediatelypreceding, 20%;

A cyclohexylamine salt of a polypropylated ame s-e4 .7 .eAn.iammon'iumisalt :of a polypropytlateda naphthalene :monosulfonic:acid,,24-,%;.; 1 ,i

A sodium salt aof oil-soluble .mahoganyapetro- Lleumgsuiiionicaacid,12%;; r

ill-A high-boiling :aromatic petroleum solvent,

.rfsopropyl alcohol,

The'zabove: proportions ,iare all wei ht percents.

.iHaving Z'thUS described my .invention-iwhatil acclaim zas new anddesire to:,secure. by Letters :Batent-is: i V

. 1 31. Agprocessffor breaking rrpetroleum'emulsions 111' thewater-in-oil :type characterized by subjecting the ,emulsionjto theactiontof :a -demulsi- :fieriincluding hydrophile synthetic :products;.said

;;hydrophilesynthetic products'being oxyalkylation :productsof (A) :analpha-beta alkylenesoxide selected; from theclass consisting ofethyleneoxide, pro pylene oxide,"buty1ene oxide,-;glycide, methyl--.glycide, methyl ,glycidyl ether, ethyhglyoidyl:

ether and propyl glycidyl ether; and --(B) an organic solvent-soluble,oxyalkylationasusceptible gpolymerization' product :of .a member o'ftheclass -;consistingof ,allylsucrose, and allylsucrose in icombinationwith other co-polymerizable yallyl :compounds; in said vcombinationtheweight per- :centagecf :allylsucrose :being not less -zthan-:and:not.-:over:90% ;'a-and:-with the:proviso that-the-hydrophilezproperties of said oxyalkylated'ideriv- :atiue :inJan: equalweight *,of' rxy'lene *are rsufficient lto'aproduce :an emulsion when:saidxylene sol-u- :tionis -shaken vigorously with one to i-threevolzumesof water.

i2. r-A-zprocessior breaking petroleum-emulsions mint-he water-ein-oiltype :characterized by'sub- :iectingthe emulsion'to the action ofg-a:demulsifier including hydrophile synthetic-products ;z;sai,d.rhydrophile gsynthetic products being :oxyalkylawtionrproducts of (-A')an alpha-betaalkylenezox- .;ide,selected from theclassconsisting-Methylene oxide, :propylene oxide, ibutylene oxide,ggl-ycide, methylglyc'ide, methyl g1ycidyl:ether,:1ethy1 zglycidyl etherand propyl :glycidyl ether; and ('B) an organic solvent-soluble,:oxyalkylationsusceptible polymerization product of ca vmemberqo'f theclass consisting of allylsucrose, and allylsucrose in combination with:other no- :polymerizable 1allyl compounds; :in 'said .combination theweight percentage c'f :allylsucrose "being not less than 10% andnotover-90%; andv withfthe proviso thatzthe molecular weight oftheoxyalkyla'tion products on anaverage statistical basis, assumingcompleteness of reaction, is in "excess of 10,000; and with the proyisothat the hydrophile properties of-said oxyalk-ylated deriv ative in anequal weighto'f xylene are sufficient to produce an emulsion when saidxylene solution is shaken vigorously with one to three volumesofwa'ter.t

f3'. The process ofcla'im Zi'Where i n-the =p'olymerized allylderivative is water-insoluble and organicsolvent-soluble.

{4. The process of claim '2 wherein the poly- -mer'ized allyl derivativeis Water-insoluble and organic solvent-soluble, and the allylsucrose ischaracterized by having at least *a plurality of allyl radicals. i

5. The process of claim 2 wherein'the polymerized allyl derivative iswater-insoluble and Organic solvent-soluble, and the allylsucrose ischaracterized by having at least a plurality of allyl radicals, and aplurality of hydroxy'l radicals.

6. A process for breaking petroleum emulsions of the water-in-oil"type-characterizedbysubject- 9:32 7 ing the-zemulsionftoaztheactionznfzza idemulsifler i including lhydrophile isynthetic izproducts;:isaid ,ishyrdrophile synthetic products :being vrzc'xyallmlation,productsiof (A) :.an:-:alpha-.beta .alkylene oxide selectediromtheclassconsisting-:ofsethyrlene soxide, 1 propylene ;oxide, ",butylene:oxide,:;glycide, V

vmethylglycide,tmethylglycidyl ether; ethylglycidyl V ether and;,propylglycidyl. ether;- and (B) :anwrganic :solvent-vsoluble,oxyalkylationasusceptible, polymerization product .of allylsucro'se :inwhich mthere is present a :plurality of allylra'dicals; sand with thefinal gproviso that the hy'drophileiprop- .ertie of said oxyalkylatedderivative:inran equal weightgof u-xylene are :suiiicient to ;product:an

:emulsion when :said xylene-solutionds eshaken :vigorouslygwith one-:tothree volumes of water;

7-; -A process for-breakingpetroleum emulsions tofrthe; water -in-.oiltype characterizedbyysubj ecting theemulsion-to theraction of 1ademulsifier including hydrophile synthetic products; said-hysdrophilesynthetic products being :oxyalkylation products of .(A).an;;a1pha-betaalkylene oxide selected fromthe class consisting of ethylene ox ide,propylene =oxide, butylene oxide, .glycide, 1 ne.thyl'glycide,methylglycidyl ether, ethylglycidyl ether and ,propylglycidyl ether;land IBXQan organic sol-ventesoluble, oxyalkylation-suscepti- 'jhle,polymerization product ro fwalllylsucroseifin which j'there'is present.a plurality of"'hy droxyl radicals v and with the final proviso thatthe hy- Idrophileproperties of .said oxylalkylated derivativeinan.equal'weight of xylene arejsufiicient to produce 'an emulsion when'saidxylene solution {is shaken vigorously with oneto 'three volumesofwa'ter;

8. A process 'for "breaking petroleum emulsions 'of the water-inoil typecharacterized {by subjectin'gthe emulsiontothe actionof a demulsifierincluding hydrophile synthetic products *saidihydrophil'e "syntheticproducts loeing oxyalkylation :9. The process -of-claim 8 wherein, the.polymerization product is xylene-soluble. v -10. The process ofclaim 8wherein the :polymerizationproduct is xylene-soluble and the averraggnumber of ,allyl groups on'a statistical basis 7 11. The process ofclaimB wherein the ;poly- .merization product .is xylene-soluble andjtheallylsucrose visessentially .penta-allylsucroseh 12. The process-ofclaim -8 whereinsthe polymerization product is xylene-soluble,thera'llylsucrose is essentially penta-allylsucrose, and poly- Vmerization the result o'fblowingby means of a'gaseous oxygen-containingmedium, 7 A,

:13, The process of claim '8 wherein thepoly "merizationproduct is'xylen'e+soluble, the 'allylsucroseisessentiallypenta allylsucrose,'polymeriza tion is the result of blowing-by means of a gaseousoxy'genecontaining medium, andsaid polymerization 'be'ing conducted'to"justs'hort'of'stringmess.

merization product is xylene-soluble, the allyl- 10 sucrose isessentially penta-allylsucrose, polymerization is the result of blowingby means of a gaseous oxygen-containing medium, and said polymerizationbeing conducted to the stage where 34 the product is stringy even in theform of a 50% solution in xylene.

' MELVIN DE GROOTE.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,307,058 Moeller Jan. 5, 19432,454,541 Bock et al. Nov. 23, 1948 2,499,365

De Groote et al. Mar. 7, 1950

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPECHARATERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIERINCLUDING HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETICPRODUCTS BEING OXYLKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDESELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE,BUTYLENE OXIDE, GLYCIDE, METHYLGLYCIDE, METHYL GLYCIDYL ETHER; ETHYLGLYCIDYL ETHER AND PROPYL GLYCIDYL ETHER; AND (B) AN ORGANICSOLVENT-SOLUBLE, OXYALKYLATION-SUSCEPTIBLE POLYMERIZATION PRODUCT OF AMEMBER OF THE CLASS CONSISTING OF ALLYLSUCROSE, AND ALLYISUCROSE INCOMBINATION WITH OTHER CO-POLYMERIZABLE ALLYL COMPOUNDS; IN SAIDCOMBINATION THE WEIGHT PERCENTAGE OF ALLYLSUCROSE BEING NOT LESS THAN10% AND NOT OVER 90%; AND WITH THE PROVISO THAT THE HYDROPHILEPROPERTIES OF SAID OXYALKYLATED DERIVATIVE IN AN EQUAL WEIGHT OF XYLENEARE SUFFICIENT TO PRODUCE AN EMULSION WHEN SAID XYLENE SOLUTION ISSHAKEN VIGOROYSLY WITH ONE TO THREE VOLUMES OF WATER.